KR20010020445A - Aqueous dispersion composition and coated articles - Google Patents

Abstract

This invention has its object to provide a provide an aqueous dispersion composition to be applied to porous construction and building materials, which is of the aqueous one-component type, hence simple and easy to apply, and at the same time has both decorative and sufficient waterproofing properties, as well as a coated article obtained by using the same. The aqueous dispersion composition of the present invention is characterized by containing (1) a repellent, (2) an organosilicon compound of the general formula (I) <CHEM> (wherein R<1n> represents a saturated alkyl group containing 1 to 18 carbon atoms and, when nn is 2 or more, the R<1n> groups may be the same or different; R<2n> represents a saturated alkyl group containing 1 to 5 carbon atoms and, when nn is 2 or more, the R<2n> groups may be the same or different; and nn represents an integer of 1 to 9), and (3) a fluorine-containing resin.

Description

Aqueous Dispersion Compositions and Paints {AQUEOUS DISPERSION COMPOSITION AND COATED ARTICLES}

Porous civil engineering building materials are widely used in various applications such as construction and building materials. Such porous civil building materials include, for example, architectural concrete, lightweight concrete, precast concrete, lightweight foamed concrete (ALC), asbestos slate, mortar, calcium silicate, pulp cement board, wool cement board, Inorganic materials-based porous civil engineering materials such as gypsum board, hard board, plaster, lead, block, tile, gypsum plaster, dolomite plaster, natural stone, artificial stone and glass wool; Organic porous materials such as wood, plywood, plywoods, particle boards, and the like.

If the porous civil engineering building materials are not subjected to a rigorous waterproofing process, the water penetrates into the interior during a long period of time, causing cracks due to expansion and the like. This may cause cracking due to expansion. In addition, when the waterproofing treatment is incomplete, a so-called wet color is generated on the surface, which causes the deterioration of the cosmetic properties.

Organosilicon compounds and the like have been conventionally used for the waterproofing agent which coats or absorbs the surface of the porous civil construction material to prevent the absorption of the material, but it is sufficient to be used under conditions where water stays on the surface of the material for a long time. It has the drawback of not being waterproof.

Japanese Laid-Open Patent Publication No. 3-232527 discloses a technique of using alkyl alkoxy silane as a permeation absorption inhibitor for concrete by aqueous phase without using a solvent. This is an aqueous alkoxy silane known as having a water-proof effect by using a specific emulsifier to achieve the prevention of pollution by an organic solvent, to obtain permeability to obtain good water resistance, but the effect of sustaining the effect over a long period of time It was weak.

There is also research on the plastering properties of porous civil engineering materials. Japanese Laid-Open Patent Publication No. 5-124880 discloses a finishing method of sequentially coating a coating material composed mainly of an aqueous silicone compound and a coating material composed of a fluororesin paint containing or not containing a pigment. According to this technique, in addition to the above-mentioned lasting effect of waterproofness, it is possible to impart plastering properties such as building concrete.

However, this technique has to be applied twice to the substrate, is not only troublesome in the field, but also remains a problem in reproducibility and quality maintainability.

The present invention provides an aqueous dispersion composition for porous civil construction materials, which has a simple one-component type of aqueous coating, and has a good abrasion and sufficient waterproofness, in consideration of the present situation, and a coating article using the same. It is intended to be.

The aqueous dispersion composition of the present invention is a powder (1), the following formula (I)

(Wherein R ¹ⁿ represents a saturated alkyl group having 1 to 18 carbon atoms and may be the same or different when nn is 2 or more; R ²ⁿ represents a saturated alkyl group having 1 to 5 carbon atoms and the same when nn is 2 or more) Nn represents an integer of 1 to 9), and an organosilicon compound (2) and a fluorine-containing resin (3).

TECHNICAL FIELD The present invention relates to an aqueous component composition and a coated article coated with the same, which are used for the surface of a porous civil engineering building material, having a waterproofing effect and a good plastering property for a long time and also having an excellent antibacterial effect.

This invention is explained in full detail below.

The aqueous dispersion composition of this invention contains a powder launching agent (1), an organosilicon compound (2), and a fluorine-containing resin (3).

First, the said powdering agent (1) is demonstrated.

The initiator (1) used in the present invention is at least one selected from a compound having a perfluoroalkyl group, a fluorine-based surfactant, a fluorine-based oil, a fluoro silicone oil, and a silicone oil. Especially, the compound which has a perfluoro alkyl group is especially preferable. These presentations are described below.

(I) perfluoroalkyl group containing compound

The homopolymer of a perfluoroalkyl group containing ethylenically unsaturated monomer, or the copolymer of this and another monomer, etc. are mentioned.

As said perfluoroalkyl group containing ethylenically unsaturated monomer, the compound etc. which are represented by a following formula are mentioned, for example.

In the formula, Rf represents a perfluoroalkyl group having 4 to 20 carbon atoms of the alkyl group; R ¹ represents hydrogen or an alkyl group having 1 to 10 carbon atoms; R ² represents an alkylene group having 1 to 10 carbon atoms; R ³ represents hydrogen or a methyl group; R ⁴ represents an alkyl group having 1 to 17 carbon atoms; n represents an integer of 1 to 10; m represents the integer of 0-10.

As another monomer copolymerizable with the said perfluoroalkyl group containing ethylenically unsaturated monomer, For example, the alkyl group has a C1-C20 alkyl (meth) acrylic-acid alkyl ester, (meth) acrylic-acid cyclohexyl ester, (meth) acrylic-acid benzyl ester, Di (meth) acrylate polyethylene glycol, N-methylol acrylamide, ethylene, vinyl chloride, vinyl fluoride, (meth) acrylic acid amide, styrene, α-methyl styrene, p-methyl styrene, alkyl group having 1 to 20 carbon atoms Vinyl alkyl ethers, halogenated alkyl vinyl ethers having 1 to 20 carbon atoms of alkyl groups, vinyl alkyl ketones having 1 to 20 carbon atoms of alkyl groups, maleic anhydride, butadiene, isoprene and chloroprene; Silyl group-containing vinyl monomers such as vinyl triethoxy silane, vinyl trimethoxy silane, γ- (methacryloxy propyl) trimethoxy silane, and the like.

Dissolving or dispersing these copolymers in an organic solvent and an aqueous medium is commercially available. For example, Unidyne TG-652 (manufactured by Daikin Corporation), Udinein TG-664 (manufactured by Daikin Corporation), and Yudinein TG- 410 (made by Daikin Corporation), etc. are mentioned.

In addition to the polymer having the perfluoroalkyl group (I), other perfluoroalkyl group-containing compounds can also be used as the starting agent of the present invention. As another perfluoroalkyl group containing compound, the following general formula

There may be mentioned (wherein, Rf, R ^1, R ^2, R ^4, n is as same as defined above) in display compound and the reaction product of the isocyanate compound or the like. As this isocyanate compound, Monoisocyanate group containing compound which is aliphatic type, alicyclic type, or aromatic type; As the polyisocyanate compound, for example, hexa methylene diisocyanate, trimethyl hexamethylene diisocyanate, hexa methylene triisocyanate, lysine ester triisocyanate, isophorone diisocyanate, hydrogenated xylene diisocyanate, toluene diisocyanate, xylene diisocyanate, diphenyl methane diisocyanate Isocyanates and the like; Moreover, trisbiuret modifications, isocyanurate modifications, triol modifications, etc. are mentioned as these modified bodies.

Moreover, as a perfluoroalkyl group containing compound which can be used as a precursor of this invention, the following general formula

And esterification reaction products of the compound represented by (wherein Rf, R ¹ , R ² , R ⁴ and n are as defined above) and a compound having a functional group as carboxylic acid or phosphoric acid.

As what is marketed, TG101 (made by Daikin Corporation) etc. is mentioned, for example.

(II) fluorine-based surfactant

The fluorine-based surfactant used in the present invention is a perfluoroalkyl group-containing surfactant or a perperoalkylene group-containing surfactant, an anionic fluorine-based surfactant, a cationic fluorine-based surfactant, an amphoteric fluorine-based surfactant, and a nonionic fluorine-based interface. Activators and the like. More specifically, Unitine DS-101 (manufactured by Daikin Industries, Ltd.), Unitine DS-202 (manufactured by Daikin Industries, Ltd.), Unitin DS-301 (manufactured by Daikin Industries, Ltd.), Unitin DS-406 (Daikin Industries, Ltd.) Production).

(III) fluorine oil

Examples of the fluorine oil used in the present invention include polymers of perfluoro polyether and chlorotrifluoroethylene, and other specific fluorinated hydrocarbon compounds. More specifically, Demnum S-20 (made by Daikin Industries Co., Ltd.), Daifloil # 20 (made by Daikin Industries Co., Ltd.), etc. are mentioned.

(IV) fluorosilicone oil

The fluorosilicone oil used in the present invention contains a fluoroalkyl group in the side chain or the terminal of the polysiloxane. More specifically, FS-1265 (made by Toray Dow Corning Silicon Co.), X-22-819 (made by Shin-Etsu Chemical Co., Ltd.), FL 100 (made by Shin-Etsu Chemical Co., Ltd.), etc. are mentioned.

(Ⅴ) Silicone oil

As silicone oil used by this invention, the viscosity in 25 degreeC is 50 cps or more, or a reactive group containing silicone oil is mentioned in a side chain or a terminal. More specifically, dimethyl silicone oil, methyl chloride silicone oil, methyl phenyl silicone oil, organic modified silicone oil, etc. are mentioned, For example, the compound etc. which are represented by the following formula are mentioned.

In the formula, R ¹² represents an alkylene group having 1 or more carbon atoms; PA represents polyalkylene oxide; x and y represent the integer of 1 or more, respectively.

More specifically, for example, PRX413 (manufactured by Toray Dow Corning Silicon Co., Ltd.), SF 8417 (manufactured by Toray Dow Corning Silicon Co., Ltd.), SF 8418 (manufactured by Toray Dow Corning Silicon Co., Ltd.), BY 16-855B ( Toray Dow Corning Silicon Co., Ltd., SF 8427 (Toray Dow Corning Silicon Co., Ltd.), SF 8428 (Toray Dow Corning Silicon Co., Ltd.), X-22-161C (made by Shin-Etsu Chemical Co., Ltd.), KF -857 (made by Shin-Etsu Chemical Co., Ltd.), KP-358 (made by Shin-Etsu Chemical Co., Ltd.), KP-359 (made by Shin-Etsu Chemical Co., Ltd.), etc. are mentioned.

Since the description of the releasing agent (1) has been completed, the organosilicon compound (2) will be described below.

The organosilicon compound (2) is represented by the general formula (I).

It does not specifically limit as a C1-C18 saturated alkyl group represented by said ^R1n , For example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group , Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, and the like, and the like, these may be linear or branched.

It does not specifically limit as a C1-C5 saturated alkyl group represented by said ^R2n , For example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc. are mentioned, These can be linear or branched form.

Nn is an integer of 1 to 20.

As said organosilicon compound (1), More specifically, for example, methyl trimethoxysilane, ethyl trimethoxysilane, propyl trimethoxysilane, butyl trimethoxysilane, pentyl trimethoxysilane, hexyl trimethoxy Silane, heptyl trimethoxysilane, octyl trimethoxysilane, nonyl trimethoxysilane, decyl trimethoxysilane, undecyl trimethoxysilane, dodecyl trimethoxysilane, tridecyl trimethoxysilane, tetradecyl tri Methoxysilane, pentadecyl trimethoxysilane, hexadecyl trimethoxysilane, heptadecyl trimethoxysilane, octadecyl trimethoxysilane, methyl triethoxysilane, ethyl triethoxysilane, propyl triethoxysilane, Butyl triethoxysilane, pentyl triethoxysilane, hexyl triethoxysilane, peptyl triethoxysilane, octyl triethoxysilane, nonyl triethoxysilane, decyl triethoxysilane, undecyl triethoxy Silane, dodecyl triethoxysilane, tridecyl triethoxysilane, tetradecyl triethoxysilane, pentadecyl triethoxysilane, hexadecyl triethoxysilane, heptadecyl triethoxysilane, oxdecyl triethoxysilane These etc. are mentioned, Especially, methyl trimethoxysilane and methyl triethoxysilane are preferable.

Moreover, the dimer of the said organosilicon compound, etc. can also be used as the organosilicon compound (2) used for this invention, As such a thing, nn is 2 in the said General formula (I), etc. are mentioned. Furthermore, nn may be an integer up to 20.

In manufacturing the aqueous dispersion composition of the present invention, the organosilicon compound (2) is emulsified and used. Such emulsification can be performed by a conventionally well-known method, For example, the method of using an emulsifier, etc. are mentioned. It does not specifically limit as said emulsifier, For example, a nonionic emulsifier, an anionic emulsifier, etc. are mentioned.

It does not specifically limit as said nonionic emulsifier, For example, as a general nonionic emulsifier, glycerol monostearate, glycerol monooleate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate , Sorbitan monotrioleate, sorbitan monoceskioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monool Latex, polyoxyethylene sorbitan monotrioleate, polyoxyethylene sorbitan monoceskioleate, polyoxyethylene sorbitol tetraoleate, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether , Polyoxyethylene oyl ether, polyoxyethylene high Higher alcohol ethers, polyoxyethylene octyl phenyl ethers, polyoxyethylene nonyl phenyl ethers, polyoxyethylene nonyl phenyl ethers, and the like.

Moreover, a fluorine-type emulsifier, a silicone type emulsifier, etc. are mentioned as said nonionic emulsifier. As said fluorine-type emulsifier, what was mentioned above by description of the term of the following fluorine-containing resin (3) is mentioned. As said silicone type emulsifier, the polyalkylene modified polydimethyl siloxane compound etc. which are represented by the following two chemical formulas are mentioned, for example.

In the formula, R represents hydrogen or an alkyl group. m2, n2, a2, b2, c2, d2, and e2 represent the integer which shows the number of repetitions.

It does not specifically limit as said anionic emulsifier, For example, sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl benzene sulfonate, sodium alkylnaphthalene sulfonate, sodium dialkyl sulfosuccinate, alkyl diphenyl ether disulfonate, alkyl phosphate diethanol Amine salt, alkyl potassium phosphate salt, polyoxyethylene lauryl ether sodium sulfate, polyoxyethylene alkyl ether sulfate triethanol amine salt, polyoxyethylene alkyl phenyl ether sodium sulfate, sodium alkanesulfonate, mixed fatty acid soda soap, semi-hardened ufat acid soda Soaps, semi-hardened carbohydrate soaps, stearic acid soda soaps, oleic acid soaps, castor oil car soaps, higher alcohol sodium sulfate, sodium salts of β-naphthalenesulfonic acid-formalin condensates, special aromatic sulfonic acid formalin condensates, special carboxylic acid type interfaces Activator, special polycar And the like dispersed in room surfactants, special polycarboxylic acid type polymer surfactant.

Although the ratio of the anionic emulsifier in all the emulsifiers is not specifically limited, 0.01-20 weight% is preferable. Any of the nonionic emulsifiers and any of the anionic emulsifiers may be used alone or in combination, or may be used in combination with a nonionic emulsifier and an anionic emulsifier, but any one of the nonionic emulsifiers and the anion It is preferable to use either of the emulsifiers in combination. Moreover, as a nonionic emulsifier, polyalkylene oxide modified polydimethyl siloxane and fluorinated alkyl group containing polyalkylene oxide are preferable.

Although the method of emulsifying the organosilicon compound (2) of this invention using the said emulsifier is not specifically limited, For example, stirring a mixture of the said organosilicon compound (2) and the said emulsifier with a homomixer etc. at high speed, It can be emulsified by dropwise addition of water thereto. After stirring in this way, when it becomes a completely uniform state, the aqueous dispersion of the emulsion phase stabilized by addition of water can be obtained. When water is added little by little, the concentration and viscosity may increase initially, an insoluble matter may form, or it may become a transparent liquid. However, when the amount of water is increased little by little, a uniform aqueous dispersion can be made.

Since the organosilicon compound (2) has been described above, the fluorine-containing resin (3) will be described below.

The said fluorine-containing resin (3) consists of an aqueous dispersion.

The said aqueous dispersion is explained in full detail later.

The said fluorine-containing resin (3) consists of fluorine-containing resin, or consists of a mixture of fluorine-containing resin and another resin. Examples of the other resins include acrylic resins, acrylic silicone resins, epoxy resins, urethane resins, ester resins, and the like, but acrylic resins are preferred in view of stability and durability of the aqueous dispersion composition of the present invention.

As is clear from the above description, in the present specification, the "fluorine-containing resin" means the "fluorine-containing resin" itself or a mixture of the "fluorine-containing resin" and "other resin". In addition, in this specification, "other resin" means an acrylic resin, an acrylic silicone resin, an epoxy resin, a urethane resin, ester resin, etc., Preferably it means only an acrylic resin.

The said acrylic resin as another resin is mentioned later in detail.

The said fluorine-containing resin has four following:

Fluorine-containing resins consisting of copolymers of fluoroolefins and vinyl monomers (2006.01)

Fluorine-containing resins consisting of copolymers of fluoroolefins (2006.01)

Fluorine-containing resins consisting of homopolymers of fluoroolefins (2006.01)

In the aqueous dispersion, the fluorine-containing resin (1), the fluorine-containing resin (2) or the fluorine-containing resin (3) and the fluorine-containing resin (4) prepared by seed polymerization with an acrylic resin are largely used. Can be divided

As is clear from the above description, in the present specification, "fluorine-containing resin" means a copolymer of one or two or more fluoroolefins and one or two or more vinyl monomers, or two or more fluoroolefins. It means a copolymer or a homopolymer of fluoroolefin. In the present specification, the "fluorine-containing resin" further includes the fluorine-containing resin (1) and the fluorine-containing resin (2) in the "aqueous dispersion '' described later in addition to the above (1) to (3). Or fluorine-containing resin (4) obtained by seed polymerization of an acrylic resin obtained by forming a composite resin in an aqueous medium by an acrylic monomer in the presence of resin particles composed of the fluorine-containing resin (3).

Hereinafter, the acrylic resin as another resin which comprises the fluorine-containing resin (3) of this invention is demonstrated.

As said acrylic resin, if a main chain is a polymer comprised from the hydrocarbon chain which originates in acrylic acid and / or methacrylic acid, it will not specifically limit, Usually, the homopolymer of an acryl-type monomer, an acryl-type monomer, and The copolymer with another monomer which has a copolymerizable ethylenically unsaturated double bond, etc. are mentioned.

As said acrylic monomer, if it contains acrylic acid and / or methacrylic acid (henceforth "(meth) acrylic acid"), it will not specifically limit, For example, acrylic acid, acrylic acid alkyl ester, methacrylic acid, methacrylic acid alkyl ester, etc. are mentioned. have.

It does not specifically limit as said (meth) acrylic-acid alkylester, For example, the C1-C18 acrylic acid alkyl ester of an alkyl group, the methacrylic acid alkyl ester of C1-C18 of an alkyl group, etc. are mentioned.

Examples of the acrylic acid alkyl ester having 1 to 18 carbon atoms of the alkyl group include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate and 2-acrylate. Ethylhexyl, cyclohexyl acrylate, n-hexyl acrylate, t-butylcyclohexyl acrylate, stearyl acrylate, lauryl acrylate and the like.

Examples of the methacrylic acid alkyl ester having 1 to 18 carbon atoms of the alkyl group include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate and methacrylic acid. t-butyl, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate, t-butylcyclohexyl methacrylate, stearyl methacrylate, lauryl methacrylate, etc. are mentioned.

The said acryl-type monomer can also be copolymerized with polyfunctional monomers, such as ethylene glycol dimethacrylate and propylene glycol dimethacrylate, for the purpose of solvent resistance and water resistance improvement.

Examples of the monomer having an ethylenically unsaturated bond copolymerizable with the acrylic acid ester and the methacrylic acid ester include the following (I) and the following (II).

(I) ethylenically unsaturated carboxylic acids such as monomers having a reactive functional group such as maleic acid, itaconic anhydride, succinic anhydride, crotonic acid; Acrylamide, methacrylamide, N-methylacrylamide, N-methylolacrylamide, N-butoxymethylacrylamide, N-methololacrylamide, N-methylmethacrylamide, N-butoxymethylmethacryl Amide compounds such as amides; Hydroxyl group-containing monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate; Epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; silanol group-containing monomers such as γ-trimethoxysilane methacrylate and γ-triethoxy silane methacrylate; Aldehyde group-containing monomers such as acrolein; Caprolactone modified hydroxy acrylate, caprolactone modified hydroxy methacrylate.

(II) other vinyl compounds such as α-olefins such as ethylene, propylene and isobutylene; Vinyl ethers such as ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), hydroxybutyl vinyl ether (HBVE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether, polyoxyethylene vinyl ether; Alkenyls such as polyoxyethylene aryl ether, ethyl aryl ether, hydroxyethyl aryl ether, aryl alcohol, and aryl ether; Vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pibarate, vinyl benzoate, VEOVA9, and VEOVA10 (manufactured by Shell); Ethylenic unsaturated carboxylic acids such as itaconic anhydride, succinic anhydride and crotonic acid; Aromatic vinyl compounds such as styrene, α-methylstyrene, and p-tert-butylstyrene; Acrylonitrile and the like.

As the monomer having an ethylenically unsaturated bond copolymerizable with the acrylic acid ester and the methacrylic acid ester, a compound containing a low molecular weight polymer or oligomer containing a hydrophilic moiety in a molecule may be used. The said hydrophilic site means the site | part which has a hydrophilic group or the site which has a hydrophilic bond, and the site | part which consists of these combinations. Although the said hydrophilic group may be any of ionic, nonionic, amphoteric, and a combination thereof, a nonionic and anionic hydrophilic group is preferable. Also known reactive emulsifiers can be used as the monomer.

As the acrylic acid ester, the monomer having an ethylenically unsaturated bond copolymerizable with the methacrylic acid ester, and a reactive emulsifier, for example, polyethylene glycol methacrylate, polypropylene glyco methacrylate, methoxypolyethylene glycol methacrylate, polyethylene Glycool acrylates, polypropylene glycol acrylates, methoxypolyethylene glycol acrylates, polyethylene glycol aryl ethers, methoxypolyethylene glycol aryl ethers, polyethylene glycol-polypropylene glycol monomethacrylates, polyethylene glycols Polytetramethylene glycomonomethacrylate, polyoxyethylene alkyl aryl phenyl ether, polyoxyethylene alkyl aryl phenyl ether sulfate, styrene sulfonate, arylalkyl sulfonate, polyethyl Glycol glycol methacrylate sulfate, alkyl aryl sulfosuccinate, bis (polyoxyethylene-polycyclic phenyl ether) methacrylated sulfate ester salt, polyoxyethylene alkyl phenyl ether acrylic acid ester, methacryloyloxy polyoxyalkylene Sulfuric acid ester salt, methacryloyloxy alkylene sulfuric acid ester salt, polyoxyethylene vinyl ether, polyoxyethylene vinyl ester, etc. are mentioned.

In order to obtain the acrylic resin of the present invention, the polymerization method for producing a homopolymer of the acrylic monomer and a copolymer of the acrylic monomer and other copolymerizable monomers is not particularly limited, and a conventionally known method such as emulsification Polymerization, suspension polymerization, block polymerization, etc. can be selected suitably and can be used. Moreover, also about the molecular weight of the polymer after superposition | polymerization, it can consider suitably and can select it.

Moreover, a conventionally well-known thing can also be suitably selected and used also for the polymerization machine, superposition | polymerization method, a polymerization initiator, a polymerization inhibitor, another adjuvant, an emulsion adjuvant, surfactant, other additives, etc. which are used in superposition | polymerization. . In selecting these, any conventionally well-known thing can be used, if the acrylic resin obtained is a suitable thing.

The amount of the acrylic resin to be mixed to form the fluorine-containing resin (3) of the present invention is preferably 0 to 90% by weight, particularly preferably 0 to 80% by weight. If the amount is too large, weather resistance and acid rain resistance deteriorate.

It does not specifically limit as said mixing method, Usually, a well-known method can be used.

This concludes the description of the acrylic resin as another resin.

The "aqueous dispersion" related to the fluorine-containing resin (3) of this invention is demonstrated below.

The aqueous dispersion has a basic structure in which fluorine-containing resin particles are dispersed in an aqueous medium. The said aqueous dispersion consists of the aqueous dispersion (A-1) of the fluorine-containing resin which seed-polymerized the acrylic resin, and the aqueous dispersion (A-2) of the fluorine-containing resin which did not seed-polymerize the acrylic resin.

The fluorine-containing resin aqueous dispersion (A-1) is obtained by forming a fluorine-based composite resin in an aqueous medium with an acrylic monomer in the presence of fluorine-containing resin particles.

Although it does not specifically limit as said aqueous medium, The thing which added the additive, the solvent, etc. which are mentioned later later to water etc. are mentioned.

In the fluorine-containing resin aqueous dispersion (A-1) which seed-polymerized the said acrylic resin, the fluorine-containing resin which comprises the said fluorine-containing resin particle is fluorine-containing resin (2) which is a copolymer of a fluoroolefin. The copolymer of the fluoroolefin is dispersed in an aqueous medium, and when the fluorine-based composite resin is formed by the acrylic monomer, it is polymerized by so-called seed polymerization. In this specification, "seed polymerization" means the reaction which superposes | polymerizes with another monomer in the aqueous medium in which resin particle exists. The said fluorine-type composite resin therefore means the seed polymer after the said seed polymerization, and the said resin particle means the seed particle in seed polymerization.

Below, the fluorine-containing resin (2) which is a copolymer of a fluoroolefin is demonstrated.

It does not specifically limit as said fluoroolefin, For example, vinylidene fluoride (VdF), tetrafluoro ethylene (TFE), chlorotrifluoro ethylene (CTFE), hexafluoro propylene (HFP), etc. are mentioned. It does not specifically limit as a copolymer of the said fluoroolefin, For example, VdF / TFE copolymer, VdF / CTFE copolymer, VdF / HFP copolymer, TFE / CTFE copolymer, TFE / HFP copolymer, CTFE / HFP copolymer , VdF / TFE / HFP copolymer, VdF / TFE / CTFE copolymer, VdF / TFE / CTFE copolymer, VdF / CTFE / HFP copolymer, VDF / TFE / HFP copolymer, VDF / CTFE / HFP copolymer, TFE / CTFE / HFP copolymer, VdF / TFE / CTFE / HFP copolymer, etc. are mentioned.

As a copolymer of the fluoroolefin which comprises the said seed particle, the VdF type copolymer which is a copolymer of fluoroolefin other than VdF and VdF is preferable, and the copolymer which contains 70 mol% or more of VdF is preferable. If VdF is 70 mol% or more, the compatibility of the seed particle and the polymer which consists of an acryl-type monomer will improve.

The average particle diameter of the seed particles is closely related to the average particle course of the fluorine-based composite resin after seed polymerization, and the seed particle size is 40 to 290 nm in order to set the average particle diameter of the fluorine-based composite resin after seed polymerization to 50 to 300 nm. It is desirable to.

The copolymer which comprises the said seed particle can be obtained by a normal emulsion polymerization method. For example, it can be prepared by emulsion polymerization of the monomer mixture containing the fluoroolefin in the presence of a fluorine-based reactive emulsifier having a hydrophilic portion of 0.01 to 1.0% by weight with respect to water and a fluorine-based emulsifier with 0 to 1.0% by weight with respect to water. have.

And 0.001 to 0.1% by weight, preferably 1.0% by weight or less, preferably 0.5% by weight or less, more preferably 0.2% by weight or less (the lower limit is usually 0.01% by weight) with respect to the fluorine-based surfactant and water. It can be prepared by emulsion polymerization of the monomer mixture containing the fluoroolefin in the presence of 0.01 to 0.05% by weight of a nonionic non-fluorine-based surfactant. The aqueous dispersions obtained by these methods can stably contain seed particles having an average particle diameter of 0.2 µm or less at a high concentration of 30 to 50% by weight.

Examples of the fluorinated reactive emulsifier having the hydrophilic moiety include CF ₂ = CF- (CF ₂ CFX) _n Y (wherein X is F or CF ₃ , Y is SO ₃ M, COOM (M is a hydrogen atom, an amine, Ammonium or alkali metal), n represents an integer), CF ₂ = CF-O (CFX) _n Y (wherein X, Y, n are the same as above), CH ² = CF-CF ^2- O (CF (CF ³ ) CF ² O) ⁿ -CF (CF ³ ) Y (wherein Y and n are the same as above), CF ₂ = CF-CF _2- O (CF (CF ₃ ) CF ₂ O) n- And those having a structure represented by CF (CF ₃ ) Y (wherein Y and n are the same as above), but n is in the range of 0 to 3 in view of solubility in water and surface activity. It is desirable to have.

More specifically, a structure of the _{CF 2 = CF-CF 2 -O} (CF (CF 3) CF 2 O) n -CF (CF 3) COOH, it is preferable that n is 0 to 2.

Polymerization temperature is 20-120 degreeC, Preferably it is 30-70 degreeC. If the polymerization temperature is lower than 20 ° C, the stability of the resulting latex is usually low. If the polymerization temperature is higher than 120 ° C, there is a tendency that a decrease in the polymerization rate due to chain transfer occurs. Although superposition | polymerization changes with kinds of a polymer, it heats normally for 5 to 100 hours under pressurization of 1.0-50 kgf / cm <2> (gauge pressure).

As said fluorine-type emulsifier used for the emulsion polymerization of the said seed particle, 1 type, 2 or more types of mixtures, etc. of a compound which contains a fluorine atom in a structure, and has surfactant activity are mentioned. For example, an acid represented by X (CF ₂ ) _n COOH (n represents an integer of 6 to 20, X represents F or a hydrogen atom) and its alkali metal salt, ammonium salt, amine salt or quaternary ammonium salt; _{Y (CH 2 CF 2) m} COOH may be mentioned that is represented by (m is an integer from 6-13, Y is F or represents a chlorine atom) acid and its alkali metal salts, ammonium salts, amine salts or quaternary ammonium salts and the like. More specifically, the ammonium salt of perfluoro octanoic acid, the ammonium salt of perfluoro nonanoic acid, etc. are mentioned. In addition, a well-known fluorochemical surfactant can also be used.

In emulsion polymerization at the time of obtaining seed particles, a small amount of nonionic non-fluorine-based surfactant can also be used in the presence of a fluorine-based surfactant, and specific examples thereof include polyoxyethylene alkyl ethers and polyoxyethylene alkyl phenyl ethers. , Polyoxyethylene alkyl esters, sorbitan alkyl esters, polyoxyethylene sorbitan alkyl esters, glycerin esters and derivatives thereof and the like.

More specifically, polyoxyethylene alkyl ethers include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, and the like. Examples of the polyoxyethylene alkyl phenyl ethers include polyoxyethylene nonyl phenyl ether and polyoxyethylene octyl phenyl ether. Examples of the polyoxyethylene alkyl esters include monolauryl acid polyethylene glycol and monooleic acid polyethylene glycol. And monostearic acid polyethylene glycol, and the like, and examples of the sorbitan alkyl esters include monolauric acid polyoxyethylene sorbitan, monopalmitinate polyoxy ethylene sorbitan, monostearic acid polyoxyethylene sorbitan, and monooleic acid polyoxy. Ethylene sorbitan and the like, and glycerin As esters, glyceryl monomyritic acid, glyceryl monostearate, glyceryl monooleate, etc. are mentioned.

Moreover, as these derivatives, polyoxyethylene alkyl amine, polyoxyethylene alkyl phenyl-formaldehyde condensate, polyoxyethylene alkyl ether phosphate, etc. are mentioned. Particularly preferred are polyoxyethylene alkyl ethers and polyoxyethylene alkyl esters, HLB values of 10 to 18, specifically polyoxyethylene lauryl ether (EO: 5 to 20. EO is ethylene oxide Unit number), and monostearic acid polyethylene glycol (EO: 6 to 10).

It does not specifically limit as said acryl-type monomer which concerns on this invention, For example, the C1-C18 acrylic acid alkyl ester of an alkyl group, the C1-C18 methacrylic acid alkyl ester of an alkyl group, and the C1-C18 methacrylic acid of an alkyl group Alkyl ester, the monomer which has an ethylenically unsaturated bond copolymerizable with this, etc. are mentioned.

Examples of the acrylate alkyl ester having 1 to 18 carbon atoms in the alkyl group include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate and 2-acrylate. Ethylhexyl, cyclohexyl acrylate, n-hexyl acrylate, t-butylcyclohexyl acrylate, stearyl acrylate, lauryl acrylate and the like.

Examples of the methacrylic acid alkyl ester having 1 to 18 carbon atoms of the alkyl group include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate and methacrylic acid. t-butyl, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate, t-butylcyclohexyl methacrylate, stearyl methacrylate, lauryl methacrylate, etc. are mentioned.

Moreover, polyfunctional monomers, such as ethylene glycol dimethacrylate and a propylene glycol dimethacrylate, can also be copolymerized for the purpose of solvent resistance and water resistance improvement.

Examples of the monomer having an ethylenically unsaturated bond copolymerizable with the acrylic acid ester and the methacrylic acid ester include the following (I) and the following (II).

(I) ethylenically unsaturated carboxylic acids such as monomers having a reactive functional group such as maleic acid, itaconic anhydride, succinic anhydride and crotonic acid; Acrylamide, methacrylamide, N-methyl acrylamide, N-methyrylol acrylamide, N-butoxymethyl acrylamide, N-methyrol methacrylamide, N-methyl methacrylamide, N-butoxymethyl methacryl Amide compounds such as amides; Hydroxyl group-containing monomers such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate; Epoxy group-containing monomers such as glycidyl acrylate and glycidyl acrylate; silanol group-containing monomers such as γ-trimethoxysilane methacrylate and γ-triethoxysilane methacrylate; Aldehyde group-containing monomers such as acrolein; Kaflolactone modified hydroxy acrylate, kaflolactone modified hydroxy methacrylate.

(II) other vinyl compounds such as α-olefins such as ethylene, propylene and isobutylene; Vinyl ethers such as ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), hydroxy butyl vinyl ether (HBVE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether, polyoxyethylene vinyl ether; Alkenyls such as polyoxyethylene aryl ether, ethyl aryl ether, hydroxy ethyl aryl ether, aryl alcohol, aryl ether; Vinyl esters such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pibarate, vinyl benzoate, VEOVA 9 and VEOVA 10 (manufactured by Shell); Ethylenically unsaturated carboxylic acids such as itaconic anhydride, succinic anhydride and crotonic acid; Aromatic vinyl compounds, such as styrene, (alpha) -methylstyrene, and p-tert- butyl styrene; Acrylonitrile and the like.

As the monomer having an ethylenically unsaturated bond copolymerizable with the acrylic acid ester and the methacrylic acid ester, a compound containing a low molecular weight polymer or oligomer containing a hydrophilic portion in the molecule may be used. The said hydrophilic site | part means the site | part which has a hydrophilic group or the site | part which has a hydrophilic bond, and the site which consists of these combinations. The hydrophilic group may be any of ionic, nonionic, amphoteric, and a combination thereof, but a nonionic and anionic hydrophilic group is preferable. Moreover, a well-known reactive emulsifier may be sufficient.

Examples of the monomer having a ethylenically unsaturated bond copolymerizable with the acrylic acid ester and the methacrylic acid ester and the reactive emulsifier include polyethylene glycol methacrylate, polypropylene glycol methacrylate, methoxypolyethylene glycol methacrylate and polyethylene. Glycool Acrylate, Polypropylene Glycol Acrylate, Methoxypolyethylene Glycool Acrylate, Polyethylene Glycol Aryl Ether, Methoxy Polyethylene Glycol Aryl Ether, Polyethylene Glycol Polypropylene Glycol Monomethacrylate, Polyethylene Glycool Poly Tetramethylene glycol monomethacrylate, polyoxyethylene alkyl aryl phenyl ether, polyoxyethylene alkyl aryl phenyl ether sulfate, styrene sulfonate, arylalkyl sulfonate, polyethylene Glycool methacrylate sulfate, alkylaryl sulfosuccinate, bis (polyoxy ethylene polycyclic phenyl ether) methacrylated sulfate ester salt, polyoxyethylene alkyl phenyl ether acrylic ester, methacryloyl oxypolyoxyalkylene sulfate ester Salt, methacryloyloxy alkylene sulfate ester salt, polyoxyethylene vinyl ether, polyoxyethylene vinyl ester and the like.

In the present invention, when the acrylic monomer is seed-polymerized in the presence of fluorine-containing resin particles, first, expansion of the acrylic monomer to fluorine-containing resin occurs, and at this point, an aqueous dispersion in which the acrylic monomer is uniformly dissolved is present. Becomes Thereafter, the acrylic monomer is polymerized by adding a polymerization initiator, thereby forming compatible particles in which molecular chains are entangled with each other. When the said acryl-type monomer is polyfunctional, you may form an interpenetrating network structure (IPN). Examples of the polyfunctional acrylic monomers include monoglycolic dimethacrylate and diglycolic dimethacrylate.

Seed polymerization of the acrylic monomer is a known method, for example, a method in which the entire amount of the acrylic monomer is put into the reaction system in the presence of fluorine-containing resin particles, a method in which a part of the acrylic monomer is added and reacted, and then the remaining one is continuously or dividedly added. And the whole quantity of an acryl-type monomer can be performed continuously. In addition, the polymerization conditions of the seed polymerization are the same as in the normal emulsion polymerization, for example, in an aqueous medium containing fluorine-containing resin particles, a surfactant, a polymerization initiator, a chain transfer agent, optionally a chelating agent, a pH adjuster and It can superpose | polymerize by adding a solvent etc. and performing reaction for 0.5 to 6 hours at the temperature which is 10-90 degreeC.

As said surfactant, anionic, nonionic, or anionic-nonionic combination can be used, and an amphoteric surfactant may be used in some cases.

As said anionic surfactant, For example, hydrocarbon type anionic interface, such as a higher alcohol sulfate ester, alkyl sulfonic acid sodium salt, alkyl benzene sulfonic acid sodium salt, succinic acid dialkyl ester, sulfonic acid sodium salt, and alkyl diphenyl ether disulfonic acid sodium salt. In addition to the active agent, fluorine-containing anionic surfactants such as fluoroalkyl carboxylate, fluoroalkyl sulfonate and fluoroalkyl sulfate esters may be mentioned.

Examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkyl phenyl esters, sorbitan alkyl esters, glycerin esters, and the like. Derivatives; and the like.

As said amphoteric surfactant, lauryl betaine etc. are mentioned, for example.

Moreover, as said surfactant, what is called a reactive emulsifier etc. which can be copolymerized with an acryl-type monomer can be used, Furthermore, such a reactive emulsifier and the said emulsifier can also be used together.

The usage-amount of the said surfactant is 0.05-5.0 weight part normally per 100 weight part of acrylic monomers.

The polymerization initiator used in the seed polymerization is not particularly limited as long as it generates a radical which can be supplied to the free radical reaction in an aqueous medium at 20 to 90 ° C, and in some cases, may be used in combination with a reducing agent. Do. As such a thing, as a water-soluble polymerization initiator, a persulfate, hydrogen peroxide, and a reducing agent are normally mentioned sodium pyrosulfite, sodium hydrogen sulfite, sodium L-ascorbate, a longgarite, etc. Examples of the oil-soluble polymerization initiators include diisopropyl peroxy dicarbonate (IPP), benzoyl peroxide, dibutyl peroxide, azobis isobutyronitrile (AIBN), and the like.

The use amount of the polymerization initiator is usually 0.05 to 2.0 parts by weight per 100 parts by weight of the acrylic monomer.

Examples of the chain transfer agent used in the seed polymerization include halogenated hydrocarbons such as chloroform and carbon tetrachloride; n-dodecyl mercaptone, tert-dodecyl mercaptone, n-octyl mercaptones and the like. The usage-amount of the said chain transfer agent is 0-5.0 weight part normally per 100 weight part of acrylic monomers.

The solvent used in the seed polymerization is used in the range of not impairing workability, disaster prevention safety, environmental stability, or manufacturing safety, for example, in the range of 20% by weight or less, for example, methyl ethyl ketone, acetone, trichloro tri Fluoroethane, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, propanol, butanol, ethyl cellosolve, butyl cellosolve, methyl carbitol, ethyl carbitol, butyl carbitol, dioxane, butyl carbitol acetate, tec Sanol, ethyl acetate, butyl acetate, etc. are mentioned.

By adding such a solvent, the expandability of the acrylic monomer with respect to the fluorine-containing resin particle may be improved.

As for the particle diameter in the aqueous dispersion of the fluorine-containing resin particle of this invention, 50-300 nm is preferable. More preferably, it is 50-200 nm.

If the particle diameter is less than 50 nm, the viscosity of the aqueous dispersion of fluorine-containing resin is significantly increased at 30% or more in which the concentration is a practical range, which causes a problem in the coating operation. When the said particle diameter exceeds 300 nm, the settling stability of the aqueous dispersion obtained will worsen, and even the resin structure of the same composition will raise the minimum film forming temperature of an aqueous dispersion.

In addition to the aqueous dispersion (A-1) described above, the aqueous dispersion according to the present invention contains an aqueous dispersion (A-2). The said aqueous dispersion (A-2) is an aqueous dispersion which does not seed-polymerize an acrylic resin.

The aqueous dispersion (A-2) has a basic structure in which fluorine-containing resin particles are dispersed in an aqueous medium. The fluorine-containing resin constituting the fluorine-containing resin particles is a fluorine-containing resin (2) composed of a copolymer of fluoroolefins or a fluorine-containing resin (1) composed of a copolymer of a fluoroolefin and a vinyl monomer. . The fluorine-containing resin (2) composed of the copolymer of the fluoroolefin is the same as that described above with respect to the aqueous dispersion (A-1).

As fluorine-containing resin (1) which consists of a copolymer of the said fluoroolefin and a vinylic monomer, Preferably it is as follows.

As said fluoroolefin which comprises the said fluorine-containing resin (1), vinyl fluoride (VF), vinylidene fluoride (VdF), tetrafluoro ethylene (TFE), chlorotrifluoro ethylene (CTFE), hexafluoro And fluoroolefins having about 2 to 4 carbon atoms such as low propylene (HFP) and trifluoro ethylene (TrFE).

As said vinyl monomer, olefins, such as ethylene, propylene, isobutylene; Vinyl ethers such as ethyl vinyl ether (EVE), cyclohexyl vinyl ether (CHVE), hydroxybutyl vinyl ether (HBVE), butyl vinyl ether, isobutyl vinyl ether, methyl vinyl ether, polyoxyethylene vinyl ether; Alkenyls such as polyoxyethylene aryl ether, ethyl aryl ether, hydroxy ethylaryl ether, aryl alcohol, aryl ether; Ethylenic unsaturated carboxyl such as vinyl acetate, vinyl lactate, vinyl butyrate, vinyl pibarate, vinyl benzoate, vinyl esters such as VEOVA 9 (manufactured by Shell Corporation) and VEOVA10 (manufactured by Shell Corporation), itaconic anhydride, succinic anhydride, crotonic acid Acids etc. are mentioned.

As fluorine-containing resin (1) which consists of a copolymer of the said fluoroolefin and a vinylic monomer, CTFE / vinyl ether copolymer, CTFE / vinyl ester copolymer, TFE / vinyl ether copolymer, TFE / ethylene copolymer, TFE / Propylene copolymer, CTFE / ethylene copolymer, CTFE / propylene copolymer, CTFE / ethylene / vinyl ether copolymer, CTFE / ethylene / vinyl ester copolymer, and copolymers thereof and modified by a small amount of copolymerizable monomer And the like.

The aqueous dispersion (A-2) is obtained by polymerizing a fluorine-containing resin constituting the fluorine-containing resin particles, for example, in a solvent, and then dispersing in water in the presence of an emulsifier to distill off the solvent. And emulsion polymerization of the fluorine-containing resin constituting the fluorine-containing resin particles in an aqueous medium, and the like. However, in order to reduce the solvent and simplify the process, a method of emulsion polymerization in an aqueous medium is preferable.

The emulsion polymerization can be carried out by the same method as that of the emulsion polymerization usually carried out. For example, in a closed container and an aqueous medium, a surfactant, a polymerization initiator, a chain transfer agent, and optionally a chelating agent, a pH adjuster and a solvent In the presence, monomers, such as a fluoroolefin and the monomer copolymerizable with a fluoroolefin, can be obtained by making it react at 10-90 degreeC for 0.5 to 40 hours.

As the surfactant, anionic, nonionic or anionic-nonionic combinations can be used, and in some cases, an amphoteric surfactant may be used.

Examples of the anionic surfactants include hydrocarbon anionic surfactants such as higher alcohol sulfate esters, alkyl sulfonic acid sodium salts, alkyl benzene sulfonic acid sodium salts, succinic acid dialkyl ester sulfonic acid sodium salts and alkyl diphenyl ether disulfonic acid sodium salts. And fluorine-containing anionic surfactants such as fluoroalkyl carboxylates, fluoroalkyl sulfonates, and fluoroalkyl sulfate esters.

Examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylphenyl esters, sorbitan alkyl esters, glycerin esters, and the like. And derivatives thereof.

As said amphoteric surfactant, lauryl betaine etc. are mentioned, for example.

Moreover, what is called a reactive emulsifier etc. can be used as said surfactant, Furthermore, such a reactive emulsifier and the said emulsifier can also be used together.

The polymerization initiator used in the emulsion polymerization is not particularly limited as long as it generates a radical which can be provided to the free radical reaction in an aqueous medium at between 10 and 90 ° C, and in some cases, may be used in combination with a reducing agent. Do. As such a thing, as a water-soluble polymerization initiator, a persulfate, a hydrogen peroxide, and a reducing agent are normally mentioned sodium pyrosulfite, sodium hydrogen sulfite, sodium L-ascorbate, a longgarite, etc. Diisopropyl peroxydicarbonate (IPP), benzoyl peroxide, dibutyl peroxide, azobisisobutylonitrile (AIBN) etc. are mentioned as an oil-soluble polymerization initiator.

As a chain transfer agent used at the time of emulsion polymerization, For example, Halogenated hydrocarbons, such as chloroform and carbon tetrachloride; and mercaptans such as n-dodecyl mercaptan, tert-dodecyl mercaptan and n-octyl mercaptan.

The solvent used in the emulsion polymerization is used in the range of not impairing workability, disaster prevention safety, environmental safety, or manufacturing safety, for example, in the range of 20% by weight or less, for example, methyl ethyl ketone, acetone, trichlorotrifluoro Ethane, methylisobutylketone, cyclohexanone, methanol, ethanol, propanol, butanol, ethyl cellosolve, butyl cellosolve, methylcarbitol, ethyl carbitol, butyl carbitol, dioxane, butylcarbitol acetate, texanol, Ethyl acetate, butyl acetate, etc. are mentioned.

This concludes the description of the "aqueous dispersion" according to the present invention.

Although repeated, the fluorine-containing resin (3) of the present invention may be a mixture of a fluorine-containing resin and another resin, so that the "aqueous dispersion" described above is used as one form of the fluorine-containing resin (3) of the present invention. When using, any aqueous dispersion becomes one of the fluorine-containing resin (3) of this invention also when it is a mixture with other resin, preferably an acrylic resin other than the said water-based carcass itself.

As described above, the description of the fluorine-containing resin (3) of the present invention has been almost completed, but of the fluorine-containing resin constituting the fluorine-containing resin (3) of the present invention, a fluorine comprising a copolymer of a fluoroolefin and a vinyl monomer Supplementary explanation is given about the containing resin (1).

Among the fluorine-containing resins of the present invention, as the fluorine-containing resin (1) consisting of a copolymer of a fluoroolefin and a vinyl monomer, more preferably, a fluorine-containing resin consisting of a copolymer of a fluoroolefin and a specific vinyl monomer. (1a).

The fluoroolefin constituting the copolymer of the fluoroolefin and the specific vinyl monomer is represented by the formula:

CF ₂ = CFX

(Wherein X represents a hydrogen atom, a fluorine atom, a chlorine atom or a trifluoromethyl group). Preferred examples of such fluoroolefins include TFE, CTFE, TrFE, and HFP. However, the aqueous dispersion composition of the present invention is free of chlorine and can form a durable, durable coating film, and the present invention. TFE is preferable at the point that the fluorine content of an aqueous dispersion composition improves and water repellency improves.

There are three specific vinyl monomers copolymerized with the fluoroolefins: (i) β-methyl-β-alkyl substituted -α-olefins, (ii) vinyl group-containing ethers, and (iii) vinyl-containing esters, Any one of these (iii), (ii) and (iii) copolymerizes with the fluoroolefin to form the fluorine resin (3), and it is also possible to use two or more kinds of these vinyl monomers. It is preferable that these are vinyl monomers having a carboxyl group-containing vinyl monomer, or vinyl monomers having a curable reactive site such as a hydroxyl group, an epoxy group, or a silyl group, and if they do not have a carboxyl group or a curable reactive site, separately from these vinyl monomers, Carboxyl group-containing vinyl monomers; It is preferable to carry the vinyl monomer which has hardening reactive site | parts, such as a hydroxyl group, an epoxy group, a silyl group, as a specific vinyl monomer which copolymerizes with the said fluoroolefin.

Said (iii) (beta) -methyl- (beta)-alkyl substituted (alpha)-olefin is a formula:

CH ₂ = CR ⁰ (CH ₃ )

In the formula, R ₀ represents an alkyl group having 1 to 8 carbon atoms. Such a thing is not particularly limited, and examples thereof include isobutylene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, and the like. desirable.

As for the content rate which (iii) (beta) -methyl- (beta)-alkyl substituted- (alpha) -olefin occupies in the copolymer of the said fluoroolefin and a specific vinyl monomer, 5-45 weight% is preferable. If it is less than 5 weight%, the weather resistance of the aqueous dispersion composition of this invention will weaken, and if it exceeds 45 weight%, manufacture of this copolymer will become difficult.

Said (ii) vinyl group containing ether is a formula;

CH ₂ = CHR ⁵

Wherein R ⁵ represents OR ¹¹ or CH ₂ OR ¹¹ (R ¹¹ represents an alkyl group having 1 to 8 carbon atoms), and is an alkyl vinyl ether or an alkyl aryl ether, which are hydroxy alkyl vinyl ethers or hydrides. as long as it has a hydroxyl group as the hydroxy alkyl allyl ether (in this case, R ¹¹ is an alkyl group having a hydroxyl group), the hydroxyl group is to act as a reaction site with the curing agent to be described later, is desirable.

The vinyl group-containing ether is not particularly limited, and for example, ethyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxy ethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2- Hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxy Hexyl vinyl ether, 2-hydroxyethyl aryl ether, 4-hydroxybutyl aryl ether, glycerol monoaryl ether and the like.

As for the content rate which the said (ii) vinyl group containing ether occupies in the copolymer of the said fluoroolefin and a specific vinyl monomer, 1-45 weight% is preferable. If it is less than 1 weight%, the hardenability of the aqueous dispersion composition of this invention will weaken, and if it exceeds 45 weight%, gelatinization will arise easily and storage stability will fall and the coating film obtained will become weak. More preferably, it is 1-30 weight%, More preferably, it is 5-15 weight%.

The said (iii) vinyl group containing ester is a formula;

CHR ²¹ = CHR ³¹

(Wherein R ²¹ represents a hydrogen atom or COOR ^41. R ³¹ represents COOR ⁴¹ or OCOR ⁴¹ ; R ⁴¹ represents an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, or a fluorine of 1 to 10 carbon atoms.) Or a phenyl group which may be substituted with an alkyl group having 1 to 8 carbon atoms; and when R ³¹ is OCOR ⁴¹ , R ²¹ is a hydrogen atom. More specifically, the formula;

CH ₂ = CH (OCOR ⁴¹ )

Vinyl carboxylate represented by the formula;

(R ⁴¹ OOC) CH = CH (COOR ⁴¹ )

The maleic acid diester or fumaric acid diester represented by this is mentioned.

It does not specifically limit as said vinyl carboxylate, For example, vinyl acetate, a vinyl propionate, a vinyl butyrate, a vinyl isobutyrate, a vinyl pivalate, a vinyl capronate, a vinyl bastic acid, a vinyl laurate, a vinyl stearate, a vinyl benzoate, pt Vinyl butylbenzoate, vinyl salicylate, vinyl cyclohexane carboxylate, vinyl hexafluoropropionate, vinyl trichloroacetate, and the like. Moreover, it does not specifically limit as said maleic acid diester or fumaric acid diester, For example, dimethyl maleic acid, diethyl maleic acid, maleic acid dipropyl, dibutyl maleic acid, maleic acid diphenyl, maleic acid dibenzyl, maleic acid ditrityl, maleic acid ditrile Fluoromethyl, ditrifluoroethyl maleate, dihexafluoropropyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, diphenyl fumarate, dibenzyl fumarate Trityl, ditrifluoromethyl fumarate, ditrifluoroethyl fumarate, dihexafluoropropyl fumarate, and the like.

As for the content rate which the said (iii) vinyl-group-containing ester occupies in the copolymer of the said fluoroolefin and a specific vinyl monomer, 1-45 weight% is preferable. If it is less than 1% by weight, the solubility and compatibility are inferior, the glass transition temperature is lowered, and if it is more than 45% by weight, it will cause weather resistance deterioration. More preferably, it is 5-40 weight%, More preferably, it is 10-30 weight%.

The carboxyl group-containing vinyl monomers described above as specific vinyl monomers other than the above (i), (ii) and (i) are the dispersibility, curing reactivity of the fluorine-containing resin (3) of the present invention, and the aqueous dispersion composition of the present invention. The adhesiveness to a base material is improved. Examples of the carboxyl group-containing vinyl monomers include those derived from crotonic acid, maleic acid, acrylic acid, methacrylic acid, itaconic acid, vinyl acetic acid, and the like. The proportion of the carboxyl group-containing vinyl monomer in the total vinyl monomer is preferably 0.01 to 10 mol%. When too small, compatibility with a hardening | curing agent will fall, and when too large, water resistance will fall.

As a vinyl monomer which has the hardening reaction site | part already mentioned as specific vinyl monomers other than said (iv), (ii), and (iii), the said hardening reaction site | part is a hydroxyl group, an epoxy group, and a silyl group. As a vinyl monomer whose said hardening reaction site | part is a hydroxyl group, the hydroxy alkyl vinyl ether, hydroxy alkyl vinyl ester, etc. which were already demonstrated by the description of said (ii) are mentioned.

Moreover, as a vinyl monomer which has another hardening reaction site | part, the epoxy-group-containing vinyl monomer described in Unexamined-Japanese-Patent No. 2-232250 and 2-232251, for example, Unexamined-Japanese-Patent No. 61-141713 The silyl group containing vinyl monomer etc. which are described in the arc etc. are mentioned.

As said epoxy group containing vinyl monomer, the epoxy vinyl or epoxy vinyl ether represented by following formula is mentioned, for example.

CH ₂ = CH-R ^53- R ⁵⁴

Wherein R ⁵³ represents -CH ₂ -O-R ⁵⁵ ,

Or R ⁵⁵ -where R ⁵⁵ represents an alkylene group, R ⁵⁴ is

(Wherein R ⁵⁶ represents a hydrogen atom or an alkyl group),

or )

As these specific examples, it is as follows, for example.

Specific examples of the silyl group-containing vinyl monomers include, for example, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tripropoxy silane, vinyl methyldimethoxy silane, vinyl dimethylmethoxy silane, vinyl methyldiethoxy silane, and vinyl tris. (β-methoxy) silane, trimethoxysilylethyl vinyl ether, triethoxysilyl ethyl vinyl ether, trimethoxy silyl butyl vinyl ether, trimethoxy silyl ethyl vinyl ether, trimethoxy silyl propyl vinyl ether, trie Methoxy silyl propyl vinyl ether, vinyl triisopropenyl oxysilane, vinylmethyl-diisopropenyloxy silane, triisopropenyloxy silyl ethyl vinyl ether, triisopropenyloxysilyl propyl vinyl ether, triisopropenyl oxysilyl Butyl vinyl ether, vinyl tris (dimethyliminooxy) silane, vinyltris (methyl-ethyliminooxy) silane, b Methylbis (methyldi-methyliminooxy) silane, vinyl dimethyl (dimethyliminooxy) silane, tris (dimethyliminooxy) silylethyl vinyl ether, methyl bis (dimethyliminooxy) silyl ethyl vinyl ether, tris ( Dimethyliminooxy) silyl butyl vinyl ether, γ- (meth) acryloyl oxy propyl trimethoxy silane, γ- (meth) acryloyl oxy propyl triethoxy silane, γ- (meth) acryloyloxypropyl Methyldimethoxysilane, γ- (meth) acryloyl oxypropyl triiso propenyl oxy silane, γ- (meth) acryloyl oxy propyltris (dimethyliminooxy) silane, γ- (meth) acryloyl oxy Propyl tris (dimethyliminooxy) silane, aryl trimethoxy silane, and the like.

Although the ratio in particular in all the vinyl monomers of the vinyl monomer which has the said hardening reaction site | part does not have regulation, 5-15 mol% is preferable. When too small, hardenability will become inadequate, when too large, gelation will occur easily and storage stability will worsen.

The copolymer of the said fluoroolefin and a specific vinyl monomer can be manufactured by superposing | polymerizing said monomer by a normal polymerization method. As such a polymerization method, for example, the method mentioned above with respect to the polymerization method of the fluorine-containing resin which comprises the seed particle in the term of the fluorine-containing resin aqueous dispersion (A-1) which seed-polymerized the acrylic resin mentioned above, etc. Can be mentioned.

This concludes the description of the fluorine-containing resin (3) of the present invention. The description so far is summarized below.

(1) The fluorine-containing resin (3) of the present invention is composed of an aqueous dispersion.

(2) The fluorine-containing resin (3) of the present invention is composed of a fluorine-containing resin or a mixture of a fluorine-containing resin and another resin.

(3) It is preferable that the said other resin which comprises the fluorine-containing resin (3) of this invention is an acrylic resin.

(4) One type of fluorine-containing resin constituting the fluorine-containing resin (3) of the present invention is a copolymer of a fluoroolefin and a vinyl monomer. Also in this case, the said fluorine-containing resin (3) consists of a fluorine-containing resin, or consists of a mixture of a fluorine-containing resin and another resin (especially acrylic resin).

(5) One type of fluorine-containing resin constituting the fluorine-containing resin (3) of the present invention is a copolymer of fluoroolefin. Also in this case, the said fluorine-containing resin (3) consists of a fluorine-containing resin, or consists of a mixture of a fluorine-containing resin and another resin (especially acrylic resin).

(6) In the case of (5) above, the copolymer of the fluoroolefin is preferably a copolymer of vinylidene fluoride and fluoroolefins other than vinylidene fluoride. Also in this case, the said fluorine-containing resin (3) consists of a fluorine-containing resin, or consists of a mixture of a fluorine-containing resin and another resin (especially an acrylic resin).

(7) In the case of (6) above, the fluorine-containing resin (3) is preferably a fluorine-containing resin seed-polymerized with an acrylic resin. Also in this case, the said fluorine-containing resin (3) consists of a fluorine-containing resin, or consists of a mixture of a fluorine-containing resin and another resin (especially acrylic resin).

The detailed description of the structure of the fluorine-containing resin (3) has been completed. When the fluorine-containing resin (3) of this invention has a hardening reaction site | part, it reacts with the said hardening reaction site | part in accordance with the objective for the purpose of improving the durability and solvent resistance of the coating film which the aqueous dispersion composition of this invention forms. You may add a hardening | curing agent. It does not specifically limit as said hardening | curing agent, For example, an isocyanate type hardening | curing agent, a melamine type hardening | curing agent, etc. are mentioned.

Since the description of the powder launching agent (1), the organosilicon compound (2), and the fluorine-containing resin (3) has been completed, the aqueous dispersion composition of the present invention containing these is described.

The aqueous dispersion composition of the present invention can be obtained by mixing the starting agent (1) with the above-described fluorine-containing resin (3) which is an aqueous dispersion of the organosilicon compound (2) and an aqueous dispersion. The said mixing can be performed by selecting a conventional method suitably, For example, it can obtain by stirring three things using a stirrer, such as a homomixer.

Said three mixing ratios are made into each solid content weight ratio,

[(Recipient (1)) + (Organic Silicon Compound (2))] / (Fluorine-containing Resin (3))

It is preferable to make the value of 1 or more. If the said value is less than 1, the surface color of the article which apply | coated the aqueous dispersion composition of this invention will become wet color, and its beauty property will be inferior.

Moreover, as solid content weight ratio,

(Stimulation (1)) / (Organic Silicon Compound (2))

It is preferable to make the value of be 0.005 or more and 200 or less. If the value is less than 0.005 or more than 200, the water resistance becomes weak.

In manufacturing the aqueous dispersion composition of this invention, in addition to the above, it can contain a suitable additive further. Such additives are not particularly limited and include, for example, pigments, preservatives, antibacterial agents, antibacterial agents, flame retardants, surface conditioners, curing catalysts, viscosity modifiers, leveling agents, ultraviolet absorbers, anti-skinning agents, dispersants, antifoaming agents and the like. Known additives commonly used and the like can be mentioned, and the amount of these additions is not particularly limited, and a conventional amount of addition can be employed.

When an antimicrobial agent (preservative, antirust agent) is added to the aqueous dispersion composition of this invention, the effect as an antiseptic and rustproof coating film can be exhibited simultaneously. Furthermore, depending on the type of the additive, it can also be applied as a waterproofing agent, a pollution prevention solvent, and the like. An aqueous dispersion composition having such an antimicrobial effect is also one of the objects of the present invention.

It does not specifically limit as said antimicrobial agent, For example, Nopcocide SN-135 (manufactured by Sanofko Corp.), Nofcoside N-54-D (manufactured by Sanovco Corp.), Marineside (Marinecide) SN-70718 (Manufactured by Sanofko Co., Ltd.), Nofcoside SN-215 (manufactured by Sanofu Co., Ltd.), Nofcoside 96 (manufactured by Sanofu Co., Ltd.), Deltop (manufactured by Takeda Chemical Co., Ltd.), Slaoff S (Takeda Chemical Co., Ltd.) Suraoff 95 (manufactured by Takeda Chemical Corporation), Deltop 110 (manufactured by Takeda Chemical Corporation), Coatside D (manufactured by Takeda Chemical Corporation), coatside 55D (manufactured by Takeda Chemical Corporation), Monicide WG (Takeda Corporation) Chemical Co., Ltd., Slough AB (Takeda Chemical Co., Ltd.), Slargen L (Takeda Chemical Co., Ltd.), Baicom AK-LS (Otsuka Chemical Co., Ltd.), Baicom AK-LS (Otsuka Chemical Co., Ltd.) Etc. can be mentioned.

The reason why the aqueous dispersion composition of the present invention has very good waterproofness and plasticity is not necessarily clear, but the excellent water repellent effect (1) and the organosilicon compound (2) in which the ratio is limited as described above, At the same time, it is considered that the fluorine-containing resin (3) contained imparts sustainability that can withstand long-term use.

As porous civil construction materials to which the aqueous dispersion composition of the present invention can be applied, for example, building concrete, lightweight concrete, precast concrete, lightweight foamed concrete (ALC), asbestos slate, mortar, calcium silicate plate, pulp cement board, wool cement Inorganic materials-based porous civil construction materials such as boards, gypsum boards, hard boards, plasters, lead, blocks, tiles, gypsum plasters, dolomite plasters, natural stones, artificial stones, and glass wool; Organic porous materials such as wood, plywood, and particle board; and the like.

The aqueous dispersion composition of the present invention can be applied to a thing containing strong moisture in addition to the above-mentioned applied article and requiring strong durability by coating. As such an article, For example, cloth, such as for a tent, a cage, a roll blind, an umbrella; Wood, such as a bench, a shelf, a fence, etc. are mentioned.

The coating article which apply | coated the aqueous dispersion composition of this invention to these materials is also one of this invention.

The method of applying the aqueous dispersion composition of the present invention to produce the coated article of the present invention is not particularly limited, and for example, spray coating by air spray or airless spray, painting by brush coating, roller coater, etc., The immersion method etc. can be employ | adopted suitably. Although the thickness of the coating film of the aqueous dispersion composition of this invention in the said coating article is not specifically limited, For example, about 1-20 g / m <2> is preferable.

Although an Example is given to the following and this invention is demonstrated to it in more detail, this invention is not limited only to these Examples.

Speech (1)

Unidine TG-410 (manufactured by Daikin Industries, Ltd.) is used.

Organosilicon Compounds (2)

20 g of n-hexyltriethoxy silane, 4 g of polyoxyethylene stearyl ether, and 0.02 g of sodium laurate are mixed and stirred at 1500 rpm at high speed, and 80 g of water is slowly added thereto to obtain a white aqueous emulsion. This is represented by the organosilicon compound (2) in Table 1.

Fluorine Resin (3)

Fluorine-containing resin (3) is produced as follows.

In a pressure-resistant reactor with an agitator content of 1 L, 500 mL of deionized water, 0.5 g of ammonium perfluorooctanoate, and CH ₂ = CF-CF ₂ -OCF (CF ₃ ) CF ₂ O-CF (CF ₃ ) COOH After adding 5.0 g of a reactive emulsifier having a structure of the above-mentioned structure, repeating the pressurization and degassing of nitrogen gas to remove the dissolved air, the mixed monomer of 74/14/12 mol% ratio of VdF / TFE / CTFE was added to the vessel at 60 ° C. Press in until the internal pressure reaches 8 kgf / ㎠. Subsequently, 1.5 g of ethyl acetate was indented, 0.2 g of ammonium persulfate was added thereto, and the mixed monomers were continuously supplied so that the internal pressure of the container was constant at 8 kgf / cm 2, and the polymerization was carried out for 45 hours. The pressure is returned to normal pressure to terminate the intermediate pressure to obtain a copolymer aqueous dispersion. As a result of elemental analysis, it was found that a copolymer of VdF / TFE / CTFE = 74/14/12 (mol%) was obtained.

70 g of the aqueous copolymer dispersion was placed in a four-necked flask with a stirring blade, a cooling tube, and a thermometer, and having four inlets, and JS2 (manufactured by Sanyo Chemical Co., Ltd.) was 0.5% by weight based on the solid content of the aqueous copolymer dispersion. Add amount in%. When heated in a water bath under stirring, and when the temperature in a container reached 80 degreeC, 10 g of methyl methacrylate (MMA), cyclohexyl methacrylate (CHMA) 1.2 g, 1.5 g of PKA 5003 (made by Japanese fats and oils), and thioglyco The emulsion in which 0.3 g of isooctyl ester of oleic acid was emulsified with a 0.5% by weight aqueous solution of JS 2 was added dropwise over 1 hour. Immediately after this, 1 mL of a 2% by weight aqueous solution of ammonium persulfate is added to initiate the reaction. 3 hours after the start of the reaction, the temperature in the vessel was raised to 85 ° C., maintained for 1 hour, cooled, the pH was adjusted to 7 with ammonia water, and then filtered through a 300 mesh wire gauze to obtain a blue-white color. Obtain a resinous aqueous dispersion. This is used in the Example as fluorine-containing resin (3).

Acrylic emulsion resin

Into a four-necked flask, 3 parts by weight of sodium lauryl sulfonate and 160 parts by weight of ion-exchanged water were added, and the temperature was raised to 60 ° C in a nitrogen stream, followed by addition of 0.5 parts by weight of ammonium persulfate and 0.2 parts by weight of sodium bisulfite. 100 parts by weight of a mixture of methyl acrylate / ethyl methacrylate / n-butyl methacrylate = 63/30/7 (mol%) is added dropwise over 3 hours. The temperature at the dropwise reaction is controlled to 60 to 70 ° C.

After completion of the dropwise addition, the reaction is continued for 2 hours in the same temperature range and the reaction is continued, followed by cooling. Thereafter, the pH is adjusted to 8-9 with 15% ammonium water to obtain a stable emulsion having a solid content of 30%. This is used as "acrylic emulsion resin."

Antimicrobial agents

A mixture of nfcoside N-54-D (manufactured by Sanofko Co., Ltd.) and marine side (Marinecide) SN-7017 (manufactured by Sanofco Co.) at a weight ratio of 10: 3 is used.

Example, Comparative Example

A slate plate is employed as the base material, and 5 g / m 2 of each test object is applied to the surface of the slate plate in solid content, and the appearance and the angle of contact with water are obtained as follows. Thereafter, after 1000 hours of sunshine weather-o-meter (SWOM) test and 2000 hours of SWOM test, the appearance and logarithmic contact angle are similarly determined. The results are shown in Table 1.

Exterior

About the surface of the slate plate which is a base material, chromaticity is measured using the measuring device by Nippon Denshoku Kogyo. After apply | coating each test object, it dries and chromaticity is similarly measured. Then, the color difference ΔE is obtained and evaluated as follows.

(o) Color difference is less than one.

ㅿ: The color difference is 1-2.

X: The color difference exceeds 2.

Logarithmic contact angle

In the same manner as above, the logarithmic contact angle before application and after application drying of each test object are obtained. The measurement is performed by the droplet method. Kyowa Kaimen Kagaku manufactured CA-DT type measuring instrument is used. The numerical value of Table 1 shows the degree (degree).

Water running test

At a height of 20 cm, 1000 ml / min of distilled water is dropped on the test plate at a right angle for 1 minute. Thereafter, the plate under test is tilted at 45 ° and left for 1 minute, and then the appearance of the drawing is visually observed. Evaluation is based on the following criteria.

ｏ: The water rolls down.

T: It becomes a drop of water, but becomes a little attached.

X: The surface becomes wet color without becoming water droplets.

Since the aqueous dispersion composition of this invention consists of the structure mentioned above, it has the outstanding waterproofness and aesthetics, and is very suitable as coating materials, such as a porous civil engineering building material.

Claims (11)

Presentation (1), Formula (I): [Formula I] (Wherein R ¹ⁿ represents a saturated alkyl group having 1 to 18 carbon atoms, which may be the same or different when nn is 2 or more; R ²ⁿ represents a saturated alkyl group having 1 to 5 carbon atoms; the same when nn is 2 or more) Nn represents an integer of 1 to 20), and an organic silicon compound (2) and a fluorine-containing resin (3). The aqueous dispersion composition according to claim 1, wherein the fluorine-containing resin (3) consists of an aqueous dispersion. The aqueous dispersion composition according to claim 1, wherein the fluorine-containing resin (3) is made of a fluorine-containing resin or a mixture of a fluorine-containing resin and another resin. The aqueous dispersion composition according to claim 3, wherein the other resin is an acrylic resin. The aqueous dispersion composition according to claim 3 or 4, wherein the fluorine-containing resin is a copolymer of a fluoroolefin and a vinyl monomer. The aqueous dispersion composition according to claim 3 or 4, wherein the fluorine-containing resin is a copolymer of fluoroolefins. 7. The aqueous dispersion composition of claim 6, wherein the copolymer of fluoroolefin is a copolymer of vinylidene fluoride and fluoroolefins other than vinylidene fluoride. The solid content weight ratio of the powder (1), the organosilicon compound (2), and the fluorine-containing resin (3) according to any one of claims 1, 2, 3, 4, 5, 6 or 7, (1)) + (organic silicon compound (2))] / (fluorine-containing resin (3)) is 1 or more, and (recipient (1)) / (organic silicon compound (2)) is 0.005 or more and 200 or less Aqueous dispersion composition. A coating article obtained by applying the aqueous dispersion composition according to claims 1, 2, 3, 4, 5, 6, 7 or 8. The coated article according to claim 9, wherein the member to be coated constituting the coated article is a porous civil construction material having a porous surface. The coated article of claim 10 wherein the porous civil building material is concrete.